DE202023104910U1 - Lutein crystal, complex oil suspension and carotenoid preparation - Google Patents

Abstract

Lutein crystal, wherein the lutein crystal is prepared according to the following steps:connecting a first line, a second line and a third line with a "Y" shaped connecting valve;mixing marigold extract with a low carbon alcohol and feeding the mixture into the first line with a first flow rate and then preheating to obtain a marigold extract solution; feeding the alcohol blend solution into the second line at a second flow rate, the ratio of the flow rate of the marigold extract solution to that of the alcohol blend solution being the first flow rate ratio; mixing the marigold extract solution and the alcohol blend solution in the third line ,Maintaining the third line at a first temperature and a first pressure and carrying out the saponification reaction to obtain the saponified reaction solution; adding acid in the saponified reaction solution to neutralize it to a first pH, then adding a complexing agent, stirring room temperature, precipitation of lutein crystals and filtering to obtain a first filter cake; andadding alkaline alcohol solution in the first filter cake, stirring at room temperature and filtering to obtain a second filter cake, adding water in the second filter cake, stirring, filtering and drying to obtain a lutein crystal.

Description

TECHNICAL FIELD

The application relates to a carotenoid product, in particular a lutein crystal, a complex oil suspension and a carotenoid preparation.

STATE OF THE ART

The carotenoids are the main source of vitamin A in the human body, have immunomodulatory, antioxidant, anti-cancer and anti-aging effects and can have positive effects on human health. However, the carotenoids are insoluble in water and have low solubility in oils and fats, and at the same time they are unstable under the influence of light, oxygen and heat, which limits the application of carotenoid preparations. In addition, for carotenoids such as lutein, the lutein can be produced by saponification, which requires the use of a large amount of alkali and a long saponification time, producing alkaline wastewater, which is not environmentally friendly.

Accordingly, there is a need to provide a lutein crystal produced by an optimized manufacturing process and a complex oil suspension and a carotenoid preparation containing the lutein crystal in order to improve the stability and application degree of the complex oil suspension and the carotenoid preparation.

CONTENT OF THE PRESENT INVENTION

One or more embodiments of the application provide a lutein crystal, the lutein crystal being manufactured according to the following steps: connecting a first conduit, a second conduit, and a third conduit to a “Y”-shaped connecting valve; mixing marigold extract with a low carbon alcohol and feeding the mixture into the first line at a first flow rate and then preheating to obtain a marigold extract solution; feeding the mixed alcohol solution into the second line at a second flow rate, wherein the ratio of the flow rate of the marigold extract solution to that of the mixed alcohol solution is the first flow rate ratio; mixing the marigold extract solution and the alcohol mixed solution in the third line, maintaining the third line at a first temperature and a first pressure, and carrying out the saponification reaction to obtain the saponified reaction solution; adding acid to the saponified reaction solution to neutralize it to a first pH, then adding a complexing agent, stirring at room temperature, precipitating lutein crystals and filtering to obtain a first filter cake; and adding alkaline alcohol solution in the first filter cake, stirring at room temperature and filtering to obtain a second filter cake, adding water in the second filter cake, stirring, filtering and drying to obtain a lutein crystal.

One or more embodiments of the application provide a complex oil suspension, the complex oil suspension comprising the above-mentioned lutein crystal, vegetable oil and phospholipids, the mass of the lutein crystal being 20%-35% of the mass of the complex oil suspension, and the mass of the vegetable oil 60%-80% of the mass of the complex oil suspension, and the mass of phospholipid represents 0.5%-5% of the mass of the complex oil suspension. One or more embodiments of the application provide a carotenoid preparation prepared by mixing, emulsifying and pelleting pretreated carotenoids and pretreated gelatinized wall material, the carotenoids comprising lutein crystals mentioned above.

BRIEF REGISTRATION OF DRAWINGS

• 1 zeigt ein Ablaufdiagramm eines Verfahrens zur Herstellung des Luteins gemäß einigen Ausführungsbeispielen der Anmeldung.
• 2 zeigt ein schematisches Diagramm einer Verbindungsleitung des „Y“-förmigen Verbindungsventils gemäß einigen Ausführungsbeispielen der Anmeldung.

This application is explained in more detail using exemplary embodiments, which are described in detail using the accompanying drawings. These embodiments are not limiting, and in these embodiments the same numbering means the same structure.

• 1 shows a flowchart of a method for producing lutein according to some exemplary embodiments of the application.
• 2 shows a schematic diagram of a connecting line of the “Y”-shaped connecting valve according to some embodiments of the application.

DETAILED REGISTRATION

In order to explain the technical solution in the exemplary embodiments of the application more clearly, the figures to be used in the explanation of the exemplary embodiments are briefly presented below. Obviously, the figures described below show only some examples or embodiments of the application, one of ordinary skill in the art can apply the present application to other similar scenarios in accordance with these drawings without any creative work. Unless apparent from the linguistic context or otherwise indicated, the same symbols in the drawings represent the same structure or operation.

As shown in this application and in the claims, the terms "a", "a piece", "a kind" and/or "the" do not specifically refer to the singular, but may also include the plural, unless: that the context clearly suggests an exception. In general, the terms "including" and "comprising" only indicate the inclusion of clearly identified steps and elements that are not an exclusive list, and the method or device may also include other steps or elements.

The carotenoids may contain lutein, which has antioxidant properties that can protect vision and delay early atherosclerosis. Current conventional processes generally use saponification to produce the lutein, but the manufacturing process uses a large amount of alkali, producing alkaline wastewater, which is not environmentally friendly, and the purity of the lutein in the manufactured product is low. Some embodiments of the present application provide a lutein crystal obtained by preparation using a tubular reaction in combination with the alcoholysis method and purification using a complexing agent.

In some embodiments of the present application, a marigold extract is mixed with a low-carbon alcohol to obtain a marigold extract solution, and then the marigold extract solution and the alcohol mixture are separately introduced into a preheating line, and the flow rate ratio of the reactants is controlled to achieve a saponification reaction at a certain temperature and a certain pressure, and an acid is added to the saponified reaction solution to neutralize the reaction solution, and a complexing agent is added to extract the lutein, and the lutein crystals are obtained by subsequent treatment. The method uses a tubular reaction to preheat the reaction material and mix the reaction material in advance, which can realize the continuous reaction of lutein production and significantly shorten the reaction time, and also uses an alcoholysis method, thereby realizing that only a small amount of alkali can be used to convert the lutein ester into the lutein, and the method of complexation can be used to directly complex and separate the lutein, and the separated lutein has a high content and a high yield, and the reaction time is short.

1 shows a flowchart of a method for producing lutein according to some exemplary embodiments of the application. Process 1000 may include the following steps.

Step S 1010: Connecting a first line, a second line and a third line with a “Y”-shaped connecting valve.

In some embodiments, the first line and the second line may be preheat lines for conveying the reaction material. As in 2 shown, the first line can be used to deliver a marigold extract solution and the second line can be used to deliver an alcohol mixed solution. In some embodiments, the third line is used to mix the reaction materials and perform a saponification reaction. In some embodiments, the first and second conduits may be straight or coiled tubes. In some embodiments, the first line and the second line may have a diameter of 0.2-2 cm. In some embodiments, the first line and the second line may have a diameter of 0.5-1.6 cm. In some embodiments, the first line and the second line may have a diameter of 1.0-1.5 cm. In some embodiments, the first line and the second line may have a length of 0.5-3 m. In some embodiments, the first line and the second line may have a length of 1.5-2.5 m. In some embodiments, the first line and the second line may have a length of 2-2.5 m. In some embodiments, the third line may be a straight one or be a coiled pipe. In some embodiments, the third line may have a diameter of 1.2-1.6 cm. In some embodiments, the third line may have a diameter of 1.0-1.5 cm. In some embodiments, the third line may have a diameter of 0.7-0.9 cm. In some embodiments, the third line may have a length of 30-100 m. In some embodiments, the third line may have a length of 3-60 m. In some embodiments, the third line may have a length of 9-20 m.

Step S1020: Mix marigold extract with a low-carbon alcohol and feed the mixture into the first line at a first flow rate and then preheat to obtain a marigold extract solution.

In some embodiments, the low carbon alcohol may be a C1-C4 low carbon alcohol. In some embodiments, the low carbon alcohol may be at least one of: anhydrous methanol, ethanol, isopropanol, n-butanol. In some embodiments, the mass ratio of the mixture of the marigold extract and the low carbon alcohol is 1:(2-10) marigold extract: low carbon alcohol. In some embodiments, the mass ratio of the mixture of the marigold extract and the low carbon alcohol is 1:(3-8) marigold extract: low carbon alcohol. In some embodiments, the mass ratio of the mixture of the marigold extract and the low carbon alcohol is 1:(5-7) marigold extract: low carbon alcohol.

The first flow rate is the flow rate of the mixed solution of the marigold extract and the low carbon alcohol (i.e. the marigold extract solution). In some embodiments, the first flow rate may be 2-800 mL/min. In some embodiments, the first flow rate may be 50-600 mL/min. In some embodiments, the first flow rate may be 100-500 mL/min. In some embodiments, the first flow rate may be 200-400 mL/min. In some embodiments, the first flow rate may be 250-300 mL/min.

The preheating temperature may be a temperature at which the reaction material in the preheating lines (i.e. the first line and the second line) is heated. In some embodiments, the preheating temperature may be 60-100°C. In some embodiments, the preheating temperature may be 70-90°C. In some embodiments, the preheat temperature may be 80-85°C.

Step S1030: Feeding the alcohol mixed solution into the second line at a second flow rate, where the ratio of the flow rate of the marigold extract solution to that of the alcohol mixed solution is the first flow rate ratio.

The second flow rate is the flow rate at which the alcohol mixture solution enters the second pipeline. In some embodiments, the second flow rate may be 2-1200 mL/min. In some embodiments, the second flow rate may be 50-1000 mL/min. In some embodiments, the second flow rate may be 100-800 mL/min. In some embodiments, the first flow rate may be 300-600 mL/min. In some embodiments, the first flow rate may be 400-500 mL/min.

In some embodiments, the mass concentration of the alcohol mixture solution may be 0.01-8%. In some embodiments, the mass concentration of the alcohol mixture solution may be 0.1-0.7%. In some embodiments, the mass concentration of the alcohol mixture solution may be 0.3-0.5%. In some embodiments, the mixed alcohol solution may contain at least one of the following solutions: sodium ethoxide-ethanol solution, sodium methoxide-methanol solution, potassium methoxide-methanol solution, potassium ethoxide-ethanol solution, sodium hydroxide-alcohol solution, potassium hydroxide-alcohol solution.

The first flow ratio is the ratio of the flow rate of the marigold extract solution to the flow rate of the alcohol mixture solution when the reaction material enters the third pipeline. In some embodiments, the first flow rate ratio may be 1:(1-5). In some embodiments, the first flow rate ratio may be 1:(2-4). In some embodiments, the first flow rate ratio may be 1:(3-4). For example, if the flow rate of the marigold extract solution is 150 mL/min, the flow rate of the alcohol blend solution is 250 mL/min.

Step S1040: Mix the marigold extract solution and the alcohol mixed solution in the third line, maintain the third line at a first temperature and a first pressure, and carry out the saponification reaction to obtain the saponified reaction solution.

2 shows a schematic diagram of a connecting line of the “Y”-shaped connecting valve according to some embodiments of the application. In some embodiments, as in 2 As shown, the marigold extract solution in the first line and the mixed alcohol solution in the second line are mixed in the third line after passing through the "Y" connection valve, and the mixed marigold extract solution and the mixed alcohol solution are mixed in the third line at a first temperature and subjected to a first pressure of a saponification reaction to obtain the saponified reaction solution.

In some embodiments, the first temperature may be 60-120°C. In some embodiments, the first temperature may be 80-110°C. In some embodiments, the first temperature may be 90-100°C. In some embodiments, the first pressure may be 0-5 MPa. In some embodiments, the first pressure may be 0.5-4 MPa. In some embodiments, the first pressure may be 1-3 MPa.

By preheating the reaction material, namely the marigold extract solution and the alcohol mixed solution, through the first line and the second line and then entering the third line to mix and carry out the saponification reaction, the marigold extract solution and the alcohol mixed solution can be made to carry out the saponification reaction quickly at a high temperature to obtain the lutein, thereby realizing the continuous reaction to produce the lutein. In addition, through this Y-connection valve connecting three pipes for mixing reaction, the saponification time can be effectively shortened, manual operation can be reduced, and labor costs can be reduced.

Step S 1050: Add acid in the saponified reaction solution to neutralize it to a first pH, then add a complexing agent, stir at room temperature, precipitate lutein crystals and filter to obtain a first filter cake.

In some embodiments, the neutralizing acid may comprise at least one of the following acids: glacial acetic acid, sulfuric acid, phosphoric acid, citric acid, hydrochloric acid, sodium dihydrogen phosphate, potassium dihydrogen phosphate. In some embodiments, the mass ratio of the acid dosage to the marigold extract is (5-10):1. In some embodiments, the mass ratio of the acid dosage to marigold extract (6-9): 1. In some embodiments, the mass ratio of the acid dosage to marigold extract (7-8): 1. In some embodiments, the first pH may be in the range of 4-8. In some embodiments, the first pH may be in the range of 6-8. In some embodiments, the first pH may be in the range of 5-7.

In some embodiments, the complexing agent may be tributyl phosphate or trioctylamine. In some embodiments, the mass ratio of the complexing agent to the marigold extract can be (0.0005-0.01):1. In some embodiments, the mass ratio of the complexing agent to the marigold extract can be (0.0005-0.005):1. In some embodiments, the mass ratio of the complexing agent to the marigold extract can be (0.001-0.0025):1.

By using the complexing agent to purify the extracted lutein crystals after the saponification reaction, high purity lutein crystals can be obtained, the yield of lutein crystals can be improved, and other organic solvents are not used for purification in order to be environmentally friendly and at the same time high purity lutein crystals to produce.

Step S1060: Adding alkaline alcohol solution in the first filter cake, stirring at room temperature and filtering to obtain a second filter cake, adding water in the second filter cake, stirring, filtering and drying to obtain a lutein crystal.

In some embodiments, the alkali in the alkaline alcohol solution may include at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, or potassium bicarbonate. In some embodiments, the alcohol in the alkaline alcohol solution may contain at least one of methanol and ethanol. In some embodiments, the mass con concentration of the alkaline alcohol solution be 0.1-2.0%. In some embodiments, the mass concentration of the alkaline alcohol solution may be 0.1-1.0%. In some embodiments, the mass of the alkaline alcohol solution is 0.5 to 5 times the mass of the marigold extract. In some embodiments, the mass of the alkaline alcohol solution is 1 to 4 times the mass of the marigold extract. In some embodiments, the dosage of the alkaline alcohol solution is 2 to 3 times the dosage of the marigold extract. In some embodiments, the mass of water added in the second filter cake may be 0.5 to 5 times the mass of the marigold extract. In some embodiments, the mass of water added in the second filter cake may be 1 to 4 times the mass of the marigold extract. In some embodiments, the mass of water added in the second filter cake may be 2 to 3 times the mass of the marigold extract. In some embodiments the stirring time can be 20-60 minutes. In some embodiments the stirring time can be 30-50 minutes. In some embodiments the stirring time can be 40-45 minutes. In some embodiments, the drying temperature may be 30-60°C. In some embodiments the drying temperature may be 40-50°C. In some embodiments, the drying temperature may be 40-45°C.

• (1) Auswählen von zwei Leitungen mit einer Länge von 2 m und einem Durchmesser von 0,8 cm als die erste Leitung und die zweite Leitung, und Verbinden dieser mit den beiden Enden des „Y“-förmigen Anschlusses (oder als „Y“-förmiges Verbindungsventil bezeichnet), wobei das andere Ende des „Y“-förmigen Anschlusses mit der dritten Leitung verbunden ist, und wobei die dritte Leitung eine Leitung mit einer Länge von 9 m und einem Durchmesser von 0,8 cm ist.
• (2) Nehmen von 200 kg Ringelblumenextrakt, Hinzufügen von 800 kg wasserfreiem Ethanol, und Pumpen unter Rühren mit einer Durchflussrate von 150 mL/min in die erste Leitung. Nehmen von 0,375kg Natriumethoxid und Lösen in 800 kg wasserfreiem Ethanol, Pumpen mit einer Durchflussrate von 250 mL/min in die zweite Leitung.
• (3) Einstellen der Reaktionstemperatur in der dritten Leitung auf 85°C und des Drucks auf 0,2 MPa für die Verseifungsreaktion und Empfangen der Reaktionslösung am Ende der dritten Leitung.

The process for producing the lutein is explained in detail below using exemplary embodiments C1-C8 and comparative examples C1-C5. It should be noted that the reaction conditions, the reaction materials and the dosages of the reaction materials in working examples C1-C8 serve only to illustrate the process for producing the lutein and do not limit the scope of the present application. The exemplary embodiments C1-C8 are exemplary embodiments in which different reaction conditions and weight ratios of the materials are used, with the comparative example C1 being an exemplary embodiment without using a tubular reaction (three lines connected by a Y-connecting valve) and the comparative example C2 is an embodiment without using three tubular reaction lines connected by a Y-connecting valve, without using an alcoholysis method and without using a complexing agent. Comparative examples C3-C5 are exemplary embodiments in which the lutein is produced using the methods from other patent applications. Comparative examples C1-C5 are comparison groups for exemplary embodiments C1-C8. Embodiment example C1

• (1) Select two lines with a length of 2 m and a diameter of 0.8 cm as the first line and the second line, and connect them to the two ends of the "Y" shaped connector (or as "Y" -shaped connection valve), the other end of the “Y”-shaped connection being connected to the third pipe, and the third pipe being a pipe with a length of 9 m and a diameter of 0.8 cm.
• (2) Take 200 kg of marigold extract, add 800 kg of anhydrous ethanol, and pump into the first line with stirring at a flow rate of 150 mL/min. Take 0.375kg of sodium ethoxide and dissolve in 800kg of anhydrous ethanol, pumping into the second line at a flow rate of 250 mL/min.
• (3) Setting the reaction temperature in the third line to 85°C and the pressure to 0.2 MPa for the saponification reaction and receiving the reaction solution at the end of the third line.

Experimental results: The liquid phase composition of the reaction solution is determined, with the transesterification rate of the lutein ester in the reactant - marigold extract - reaching 99.4%, and with 0.6% of the lutein ester remaining and the saponification time is 13 min.

Example C2

• (1) Select two lines with a length of 2 m and a diameter of 0.8 cm as the first line and the second line, and connect them to the two ends of the "Y" shaped connector (or as "Y" -shaped connection valve), the other end of the “Y”-shaped connection being connected to the third pipe, and the third pipe being a pipe with a length of 54 m and a diameter of 1.4 cm.
• (2) Take 20 kg of marigold extract, add 60 kg of anhydrous ethanol, and pump into the first line with stirring at a flow rate of 200 mL/min. Take 0.75kg of potassium ethoxide and dissolve in 80kg of anhydrous ethanol, pump into the second line at a flow rate of 300mL/min.
• (3) Setting the reaction temperature in the third line to 85°C and the pressure to 0.2 MPa for the saponification reaction and receiving the reaction solution at the end of the third line.

Experimental results: The liquid phase composition of the reaction solution is determined, with the transesterification rate of the lutein ester in the reactant - marigold extract - reaching 99.73%, and with 0.3% of the lutein ester remaining and the saponification time is 8 min.

Example C3

• (1) Select two lines with a length of 3 m and a diameter of 0.6 cm as the first line and the second line, and connect them to the two ends of the "Y" shaped connector (or as "Y" -shaped connection valve), the other end of the “Y”-shaped connection being connected to the third pipe, and the third pipe being a pipe with a length of 48 m and a diameter of 1.6 cm.
• (2) Take 20000 kg of marigold extract, add 80000 kg of anhydrous methanol, and pump into the first line with stirring at a flow rate of 300 mL/min. Take 50 kg of sodium methoxide and dissolve in 80000 kg of anhydrous methanol, pump at a flow rate of 500 mL/min into the second line.
• (3) Setting the reaction temperature in the third line to 110°C and the pressure to 1 MPa for the saponification reaction and receiving the reaction solution at the end of the third line.

Experimental results: The liquid phase composition of the reaction solution is determined, with the transesterification rate of the lutein ester in the reactant - marigold extract - reaching 98.15%, and with 0.2% of the lutein ester remaining and the saponification time is 7 min.

Example C4

• (1) Select two lines with a length of 3 m and a diameter of 0.8 cm as the first line and the second line, and connect them to the two ends of the "Y" shaped connector (or as "Y" -shaped connection valve), the other end of the “Y”-shaped connection being connected to the third pipe, and the third pipe being a pipe with a length of 96 m and a diameter of 1.6 cm.
• (2) Take 200 kg of marigold extract, add 800 kg of anhydrous ethanol, and pump into the first line with stirring at a flow rate of 600 mL/min. Take 0.2 kg of sodium hydroxide and dissolve in 800 kg of anhydrous ethanol, pump at a flow rate of 1000 mL/min into the second line.
• (3) Setting the reaction temperature in the third line to 90°C and the pressure to 2 MPa for the saponification reaction and receiving the reaction solution at the end of the third line.

Experimental results: The liquid phase composition of the reaction solution is determined, with the transesterification rate of the lutein ester in the reactant - marigold extract - reaching 99.73%, and with 0.2% of the lutein ester remaining and the saponification time is 7 min.

It can be seen by comparing the embodiments C1-C4 that the transesterification rates of the lutein esters obtained from the saponification reaction using the tubular reaction are all above 98% and the saponification time is less than 13 min, indicating that at the use of the tubular reaction due to the fact that the preheating lines (i.e. the first line and the second line) have a certain length (e.g. 2 m) and the preheating lines are maintained at a preheating temperature (e.g. 85 ° C), the reaction materials as they pass through can be preheated in advance by the preheating pipe, which facilitates the subsequent rapid saponification of the lutein esters to obtain the lutein under high temperature conditions, and using the alcoholysis method, it is possible to use only a small amount of alkali to convert the lutein ester into the lutein. In the alcoholysis method, the lutein ester undergoes a decomposition reaction with the alcohol to obtain the lutein, and in the process, anhydrous short-chain alcohol is used as the main reactant for the decomposition of the lutein ester and the alkali is used as a catalyst, that is, only a small amount of alkali is required to be used in the process, which not only shortens the saponification time but also reduces labor and raw material costs

Example C5

• (1) Collecting the reaction solution of Embodiment C1, adding glacial acetic acid dropwise into the reaction solution, adjusting the pH to 8, adding 0.1 kg of tributyl phosphate, stirring at room temperature, and precipitating the lutein crystal complex.
• (2) Prepare a 0.5% sodium hydroxide solution, add it in the lutein complex, stir at room temperature for 30 min and then filter, wash the lutein crystals with water and dry the filter cake at 40 ° C. The content of lutein crystals in the product obtained is 97.3% and the yield reaches 94%. Example C6
• (1) Collecting the reaction solution of embodiment C2, adding glacial acetic acid dropwise into the reaction solution, adjusting the pH to 8, adding 0.1 kg of tributyl phosphate, stirring at room temperature, and precipitating the lutein crystal complex.
• (2) Prepare a 1% sodium hydroxide solution, add it in the lutein complex, stir at room temperature for 30 min and then filter, wash the lutein crystals with water and dry the filter cake at 40°C. The content of lutein crystals in the product obtained is 92.3% and the yield reaches 88%. Example C7
• (1) Collecting the reaction solution of embodiment C3, adding hydrochloric acid dropwise into the reaction solution, adjusting the pH to 7, adding 10kg of tributyl phosphate, stirring at room temperature, and precipitating the lutein crystal complex.
• (2) Prepare a 1.3% potassium hydroxide solution, add it in the lutein complex, stir at room temperature for 30 min and then filter, wash the lutein crystals with water and dry the filter cake at 40 ° C. The content of lutein crystals obtained is 94.67% and the yield reaches 92%. Example C8
• (1) Collecting the reaction solution of embodiment C4, adding concentrated sulfuric acid dropwise into the reaction solution, adjusting the pH to 6, adding 0.5 kg of trioctylamine, stirring at room temperature, and precipitating the lutein crystal complex.
• (2) Prepare a 1.8% sodium hydroxide solution, add it in the lutein complex, stir at room temperature for 30 min and then filter, wash the lutein crystals with water and dry the filter cake at 40 ° C. The content of lutein crystals obtained is 95.57% and the yield reaches 90%.

It can be seen by comparing the exemplary embodiments C5-C8 that the lutein crystals can be complexed directly with a complexing agent and separated and the content of the separated lutein crystals is more than 92% and the yield reaches more than 88%. The extraction of lutein by complexation does not require the use of organic solvents for extraction, so it is environmentally friendly, and it can effectively reduce the post-treatment process, shorten the production time and improve the production efficiency of lutein crystals.

Comparative example C1

• (1) 200 kg Ringelblumenextrakt werden in einen Reaktionskessel gegeben, 4 kg Natriumhydroxid und 1200 kg wasserfreies Ethanol werden hinzugefügt, und die Reaktion erfolgt unter Rühren für 3 Stunden bei 60°C, und die Reaktionslösung wird am Ende der Reaktion erhalten, und die Flüssigphasenzusammensetzung der Reaktionslösung wird bestimmt, und die Umesterungsrate der Luteinester im Reaktanten - Ringelblumenextrakt beträgt 99,73%, und 0,27% der Luteinester bleiben übrig.
• (2) tropfenweise Hinzufügen von Eisessig in der erhaltenen Reaktionslösung, Einstellen des pH-Werts der Reaktionslösung auf 8, Hinzufügen von 0,1 kg Tributylphosphat, Rühren bei Raumtemperatur und Filetieren, um den ausgefällten Luteinkristallkomplex zu erhalten.
• (3) Herstellen einer 1,3%igen Kaliumhydroxidlösung, Hinzufügen im Luteinkomplex, Rühren bei Raumtemperatur für 30 min und anschließendes Filtrieren, Waschen der Luteinkristalle mit Wasser und Trocknen des Filterkuchens bei 40°C. Der Gehalt an Luteinkristallen im erhaltenen Produkt beträgt 93,11% und die Ausbeute erreicht 88,02%.

Tabelle 1: Umesterungsrate der Luteinester und verbleibender Anteil der Luteinester nach verschiedenen Reaktionszeiten Reaktionszeit Umesterungsrate des Luteinesters Verbleibender Anteil des Luteinesters 1h 84.72% 15.28% 2h 90.94% 9.06% 3h 99.73 % 0.27%

• (1) 200 kg of marigold extract are placed in a reaction kettle, 4 kg of sodium hydroxide and 1200 kg of anhydrous ethanol are added, and the reaction is carried out with stirring for 3 hours at 60 ° C, and the reaction solution is obtained at the end of the reaction, and the liquid phase composition of the reaction solution is determined, and the transesterification rate of the lutein esters in the reactant - marigold extract is 99.73%, and 0.27% of the lutein esters remain.
• (2) adding glacial acetic acid dropwise in the obtained reaction solution, adjusting the pH of the reaction solution to 8, adding 0.1 kg of tributyl phosphate, stirring at room temperature and filleting to obtain the precipitated lutein crystal complex.
• (3) Prepare a 1.3% potassium hydroxide solution, add it in the lutein complex, stir at room temperature for 30 min and then filter, wash the lutein crystals with water and dry the filter cake at 40 ° C. The content of lutein crystals in the product obtained is 93.11% and the yield reaches 88.02%.

Table 1: Transesterification rate of the lutein esters and remaining proportion of lutein esters after different reaction times reaction time Transesterification rate of the lutein ester Remaining portion of the lutein ester 1h 84.72% 15.28% 2h 90.94% 9.06% 3h 99.73% 0.27%

In comparative example C1, as shown in Table 1, the marigold extract is added to the reaction kettle for reaction, the transesterification rate of the lutein ester is 84.72% after the reaction for one hour, the remaining proportion of the lutein ester is 15.28%, the Transesterification rate of lutein ester is 90.94% after the reaction for 2 hours, the remaining proportion of lutein ester is 9.06%, and the saponification time reaches 3 hours before the transesterification rate of lutein ester reaches 99.73%, and the remaining proportion of lutein ester is 0.27%. By comparing the comparative example C1 and the exemplary embodiment C4, the transesterification rate of the lutein ester in comparative example C1 reaches 99.73% after the reaction for 3 hours, while the transesterification rate of the lutein ester in the exemplary embodiment C4 reaches 99.73% after the saponification time for only 7 min , when the reaction is carried out through the tubular reaction, indicating that at high temperature, the reaction can be carried out quickly to obtain the lutein when the pipes connected by a Y-shaped connecting valve are used for the tubular reaction, to which Way, the continuous reaction to produce the lutein is realized to significantly shorten the reaction time, at the same time, the tubular reaction reduces the manual operation and reduces the labor cost.

Comparative example C2

• (1) 200 kg Ringelblumenextrakt werden in einen Reaktionskessel gegeben, 50 kg Natriumhydroxid und 1200 kg Ethanol werden hinzugefügt, und die Reaktion erfolgt unter Rühren für 3 Stunden bei 60°C, und die Reaktionslösung wird am Ende der Reaktion erhalten, und die Flüssigphasenzusammensetzung der Reaktionslösung wird bestimmt, und die Umesterungsrate der Luteinester beträgt 99,61%, und 0,39% der Luteinester bleiben übrig.
• (2) tropfenweise Hinzufügen von Eisessig in der erhaltenen Reaktionslösung, Einstellen des pH-Werts der Reaktionslösung auf 6-7, Hinzufügen von 1000 kg Wasser, Rühren für 30 min und Filtrieren, um Lutein-Rohkristalle zu erhalten, 800 kg 95%iges Ethanol werden zu den Lutein-Rohkristallen zugegeben, die Temperatur des Reaktionskessels wird bei 45-50°C gehalten, und die Mischung wird für 30 min gerührt und filtriert, um einen Filterkuchen zu erhalten. Der Filterkuchen wird bei 40°C getrocknet, und der Gehalt an Luteinkristallen beträgt 88,52% und die Ausbeute erreicht 83,74%.

Tabelle 2: Umesterungsrate der Luteinester und verbleibender Anteil der Luteinester bei verschiedenen Reaktionszeiten Reaktionszeit Umesterungsrate des Luteinesters Verbleibender Anteil des Luteinesters 1h 77.22% 22.78% 2h 94.27% 5.73% 3h 99.61 % 0.39%

• (1) 200 kg of marigold extract are placed in a reaction kettle, 50 kg of sodium hydroxide and 1200 kg of ethanol are added, and the reaction is carried out with stirring for 3 hours at 60°C, and the reaction solution is obtained at the end of the reaction, and the liquid phase composition of the Reaction solution is determined, and the transesterification rate of lutein esters is 99.61%, and 0.39% of lutein esters remains.
• (2) Add glacial acetic acid dropwise in the obtained reaction solution, adjust the pH of the reaction solution to 6-7, add 1000 kg of water, stir for 30 min and filter to obtain lutein crude crystals, 800 kg of 95% ethanol are added to the crude lutein crystals, the temperature of the reaction kettle is maintained at 45-50°C, and the mixture is stirred for 30 min and filtered to obtain a filter cake. The filter cake is dried at 40°C, and the content of lutein crystals is 88.52% and the yield reaches 83.74%.

Table 2: Transesterification rate of the lutein esters and remaining proportion of the lutein esters at different reaction times reaction time Transesterification rate of the lutein ester Remaining portion of the lutein ester 1h 77.22% 22.78% 2h 94.27% 5.73% 3h 99.61% 0.39%

In comparative example C2, as shown in Table 2, the marigold extract is added to the reaction kettle for reaction, the transesterification rate of the lutein ester is 77.22% after the reaction for one hour, the remaining proportion of the lutein ester is 22.78%, the Transesterification rate of lutein ester is 94.27% after the reaction for 2 hours, the remaining proportion of lutein ester is 5.73%, and the saponification time reaches 3 hours before the transesterification rate of lutein ester reaches 99.61%, and the remaining proportion of lutein ester is 0.39%. Compared with Comparative Example C1, Comparative Example C2 uses 50 kg of sodium hydroxide, but the transesterification rate of lutein ester is lower than that of Comparative Example C1, which only uses 4 kg of sodium hydroxide, indicating that the production of lutein crystals by the alcoholysis (decomposition) method of the lutein ester by ethanol) in comparative example C1 can reduce the alkali dosage and at the same time, the reaction in producing lutein crystals by the alcoholysis method is more thorough and the utilization rate of lutein ester can be improved.

By comparing exemplary embodiment C4 and comparative example C2, it can be seen that the alkali dosage of exemplary embodiment C4 is lower (for the same reaction of 200 kg of marigold extract, 1.2 kg of sodium hydroxide is used in exemplary embodiment C4 and 50 kg of sodium hydroxide is used in comparative example C2), the saponification time is shorter (the saponification time of the exemplary embodiment C4 is 7 min and that of the comparative example C2 is 3 h) and the transesterification rate of the lutein ester is higher (the transesterification rate of the lutein ester in the exemplary embodiment C4 is 99.73% and the transesterification rate of the lutein ester in the comparative example C2 is 99.61%), indicating that the use of tubular reaction combined with the alcoholysis method to produce lutein crystals in Embodiment C4 is able to reduce the alkali dosage, which is environmentally friendly while saving the cost and reaction time significantly shortened and thus improved economic efficiency.

In comparison to the exemplary embodiments C5-C8, the lutein in comparative example C2 is not extracted by complexing with a complexing agent, but rather the lutein is extracted using 95% ethanol, and the content of lutein crystals in the product is 88.52% and the yield reaches 83.74%, and both of these are lower than the content of lutein crystals and the yield in the exemplary embodiments C5-C8, in which the lutein is extracted by complexing with a complexing agent. This indicates that the complexation method can better separate the lutein by complexation, improve the lutein crystal content and yield, avoid the use of a large amount of organic solution for extraction, and eliminate the need for operations such as washing with solvents or Performing crystallization at a later stage to improve the purity of the lutein can further reduce.

In comparison to the embodiments C1-C4, the saponification times of the comparative example C1 and the comparative example C2 are each 3 h, which indicates that using the tubular reaction of the embodiments C1-C4, the reaction time for the production of the lutein from lutein esters can be shortened.

Compared to the embodiments C1-C4, in the comparative example C2, 50 kg of sodium hydroxide is used for 200 kg of marigold extract, and the transesterification rate of the lutein ester is only 77.22% after the reaction for one hour, while in the embodiment C1 only 0.375 kg of sodium ethoxide for the reaction of 200 kg of marigold extract can be used and the transesterification rate of the lutein ester after the reaction for 13 minutes reaches 99.4%, in exemplary embodiment C2 only 0.75 kg of potassium ethoxide can be used for the reaction of 20 kg of marigold extract and the transesterification rate of the lutein ester after the reaction for 99.73% is achieved in 8 minutes, in exemplary embodiment C3 only 50 kg of sodium methoxide are used for the reaction of 20,000 kg of marigold extract and the transesterification rate of the lutein ester reaches 98.15% after the reaction for 7 min, and in exemplary embodiment C4 only 1.2 kg Sodium hydroxide was used for the reaction of 200 kg of marigold extract and the transesterification rate of the lutein ester reached 99.73% after the reaction for 7 min. This indicates that a large amount of sodium hydroxide is used for the reaction in Comparative Example C2, while the lutein crystals in Examples C1-C4 are prepared using the alcoholysis method, which can reduce the alkali dosage when producing the same mass of lutein crystals and at the same time a higher transesterification rate of the lutein ester can be achieved in a shorter reaction time, resulting in a more thorough reaction and improving the utilization rate of the lutein ester.

Compared to embodiments C5-C8, the lutein content and yield are lower in comparative example C2, in which the lutein is extracted without complexing agents, indicating that the extraction of lutein by the method of complex formation in embodiments C1-C4 increases the lutein crystal content and can improve the yield, avoid the use of a large amount of organic solution for extraction, and further reduce the need to perform operations such as solvent washing or crystallization at a later stage to improve the purity of lutein.

Comparative example C3

• (1) Vorbereiten von 68,62 kg Luteinxtrakt mit 16,023% Lutein-Gehalt und Warmhalten bei 40°C. Zubereiten von 37,28 kg Kaliumhydroxidlösung mit einer Massenkonzentration von 35,0% und Herstellen mit 82,02 L 95%iger Ethanollösung zu einer alkoholischen Basislösung. In der Verseifungsanlage werden zunächst 30,0 kg alkoholische Basislösung und 20,0 kg Luteinextrakt hinzugefügt, Erwärmen auf 60°C und Warmhalten, Vorverseifen für 1,5 h, um eine verseifte Luteinextraktmischung zu erhalten.
• (2) Die effektive Verseifungskapazität der Verseifungsanlage beträgt 20 kg, wobei in der verseiften Luteinextraktmischung der Luteinextrakt und die alkoholische Basislösung mit einer Zugabegeschwindigkeit von 16,27 kg bzw. 24,41 kg pro Stunde hinzugefügt werden und sie 3 Stunden lang kontinuierlich zugeführt werden, und die schnelle kontinuierliche Verseifung dauert 29,5 min, um die Lutein-Verseifungslösung zu erhalten.
• (3) Die Lutein-Verseifungslösung wird mit erhitztem Wasser verdünnt und filtriert, der Filterkuchen wird vakuumgetrocknet und wiegt 11,01 kg, der Gesamtcarotinoidgehalt beträgt 87,32% durch die UV-Detektion, und die Ausbeute erreicht 87,19%.

Production of lutein according to the in CN106316909A described procedure.

• (1) Prepare 68.62 kg of lutein extract with 16.023% lutein content and keep warm at 40°C. Prepare 37.28 kg of potassium hydroxide solution with a mass concentration of 35.0% and make an alcoholic base solution with 82.02 L of 95% ethanol solution. In the saponification system, 30.0 kg of alcohol base solution and 20.0 kg of lutein extract are first added, warmed to 60 ° C and kept warm, pre-saponification for 1.5 h to obtain a saponified lutein extract mixture.
• (2) The effective saponification capacity of the saponification plant is 20 kg, in which the lutein extract and the alcoholic base solution are added to the saponified lutein extract mixture at an addition rate of 16.27 kg and 24.41 kg per hour, respectively, and they are fed continuously for 3 hours, and the rapid continuous saponification takes 29.5 min to obtain the lutein saponification solution.
• (3) The lutein saponification solution is diluted with heated water and filtered, the filter cake is vacuum dried and weighs 11.01kg, the total carotenoid content is 87.32% by UV detection, and the yield reaches 87.19%.

Compared to the embodiments C1-C8, in the comparative example C3, no tubular reaction is carried out and no complexing agent is used, in the manufacturing process of the comparative example C3, there is a pre-saponification process before the start of the continuous saponification, the pre-saponification lasts 1.5 h, and the continuous saponification takes approximately 30 min, the total time is 2 h, the saponification time is too long, and the pre-saponification process is realized by forced mixing equipment, which is complicated and requires cumbersome operation.

Comparative example C4

Production of lutein according to the in CN101260071A described procedure. Weigh 60 g lutein extract, 120 mL isopropanol, 60 mL methanol, add in the saponifier, weigh 14 g potassium hydroxide and 6 g vitamin C, add in the mixing system, mix with sufficient stirring, saponify at 70 ° C for 6 h, introduce of nitrogen into the saponification system and distillation at reduced pressure. In the concentrate obtained, 250 ml of water is added, stirring for 40 min at room temperature, transferred to a separatory funnel, adding 280 ml of dichloromethane to extract the lutein, forming a dichloromethane layer and an aqueous layer, the aqueous phase is washed until it is colorless and neutral to obtain the dichloromethane layer and the aqueous phase, which do not contain water-soluble impurities. To separate the ester fatty acid soap, calcium chloride is added to the aqueous phase, the separated ester fatty acid soap is combined and filtered, the filter cake is washed with dichloromethane, the filtrate is incorporated into the dichloromethane layer without water-soluble impurities and then the solvent is recovered by distillation under reduced pressure, to obtain the raw lutein to which 14 g of calcium chloride is added. A solvent mixture of 24 ml of ethyl acetate and petroleum ether is added to the crude lutein, stirred for 30 min at room temperature, filtered under reduced pressure, and then washed the filter cake with anhydrous methanol until the filtrate is colorless to obtain lutein crystals. After vacuum drying at 50°C for 72 hours, 4.0131 g of lutein crystals are obtained, and the all-trans-lutein content is 92.71% by high-performance liquid chromatography.

Compared with Embodiments C1-C8, in Comparative Example C4, no tubular reaction is carried out and no complexing agent is used, and the manufacturing process in Comparative Example C4 has a saponification time of up to 6 hours, which is too long, therefore there is a low production capacity, and the use of a large amount of potassium hydroxide and the use of methylene chloride as an extraction solvent are not environmentally friendly, and the recovery and disposal of solvents are cumbersome.

Comparative example C5

• (1) Bei 33°C werden 100 g Luteinextrakt (Luteinestergehalt von 32%) in 250 mL Dichlormethanlösung gelöst, Rühren und Refluxieren für 0,5 h, und Zentrifugieren, um unlösliche Bestandteile zu entfernen und eine Zentrifugallösung zu erhalten.
• (2) In der erhaltenen Zentrifugenlösung werden 250 mL Methanol hinzugefügt, Rühren und Refluxieren für 0,5 h bei 33°C, Stehenlassen und Kristallisieren nach der Bildung einer homogenen Lösung bei 10°C für 10 h, Filtrieren, um den Filterkuchen I (rohen Luteinester) zu erhalten, und das Filtrat wird zurückgewonnen.
• (3) Das erhaltene Filtrat wird in einen Reaktionskessel überführt, bei 40°C wird das niedrig siedende Lösungsmittel Dichlormethan zurückgewonnen, in der verbleibenden Lösung werden 350 mL Lösungsmittel n-Hexan und 13 g festes Natriumhydroxid hinzugefügt, und der Stickstoff wird zum Schutz gefüllt, Verseifung bei 50°C für 2,5 h, um die Verseifungslösung zu erhalten.
• (4) In der erhaltenen Verseifungslösung werden 600 mL entionisiertes Wasser hinzufügt, Rühren und Erwärmen für 0,5 h bei 45°C, Einstellen des pH-Werts mit Essigsäure auf 7,4 und Filtrieren, um den Filterkuchen II (rohes Lutein) zu erhalten.
• (5) Waschen des Filterkuchens I (roher Luteinester) und des Filterkuchens II (rohes Lutein) mit einer wässrigen Ethanollösung (Isopropanol:Wasser ist 1:1) und Trocknen unter Vakuum bei 25°C und -0,095 MPa für 10 h, um 24,93 g Luteinester und 2,71 g Lutein zu erhalten. Durch die Messung mittels eines UV-Vis-Spektralphotometers beträgt die Reinheit des Luteinester 86,68% und die des Luteins 89,01%; durch die Messung mittels der Hochleistungsflüssigkeitschromatographie beträgt die Reinheit des All-trans-Luteinesters 91,38% und die des All-trans-Luteins 92,16%. Durch die Berechnung beträgt der Gesamtnutzungsgrad der Rohstoffe 93,51%.

Production of lutein according to the in CN106748947A described procedure.

• (1) At 33°C, 100 g of lutein extract (lutein ester content of 32%) is dissolved in 250 mL of dichloromethane solution, stirring and refluxing for 0.5 h, and centrifuging to remove insoluble components and obtain a centrifugal solution.
• (2) In the obtained centrifuge solution, 250 mL of methanol is added, stirring and refluxing for 0.5 h at 33 ° C, allowing to stand and crystallizing after forming a homogeneous solution 10°C for 10 h, filter to obtain filter cake I (crude lutein ester), and the filtrate is recovered.
• (3) The obtained filtrate is transferred to a reaction kettle, at 40 ° C, the low-boiling solvent dichloromethane is recovered, in the remaining solution, 350 mL of solvent n-hexane and 13 g of solid sodium hydroxide are added, and the nitrogen is filled for protection, Saponification at 50°C for 2.5 h to obtain the saponification solution.
• (4) In the resulting saponification solution, 600 mL of deionized water is added, stirring and heating for 0.5 h at 45 ° C, adjusting the pH to 7.4 with acetic acid and filtering to obtain the filter cake II (crude lutein). receive.
• (5) Washing the filter cake I (crude lutein ester) and the filter cake II (crude lutein) with an aqueous ethanol solution (isopropanol:water is 1:1) and drying under vacuum at 25 ° C and -0.095 MPa for 10 h to 24 .93 g of lutein esters and 2.71 g of lutein. When measured using a UV-Vis spectrophotometer, the purity of the lutein ester is 86.68% and that of the lutein is 89.01%; As measured by high-performance liquid chromatography, the purity of the all-trans-lutein ester is 91.38% and that of the all-trans-lutein is 92.16%. By calculation, the total utilization rate of raw materials is 93.51%.

Compared with Embodiments C1-C8, the manufacturing method in Comparative Example C5 uses methylene chloride as an extraction solvent, which is not environmentally friendly, and the saponification time is 2.5 hours, which is a long saponification time. Furthermore, in the manufacturing process of Comparative Example C5, the lutein esters in marigold extract need to be purified before saponification, which is a complicated process.

Some embodiments of the application further provide a complex oil suspension. The complex oil suspension includes the above-mentioned lutein crystals, a vegetable oil and a phospholipid.

In some embodiments, the mass of the lutein crystals may be 20%-35% of the mass of the complex oil suspension. In some embodiments, the mass of the lutein crystals may be 23%-32% of the mass of the complex oil suspension. In some embodiments, the mass of the lutein crystals may be 25%-30% of the mass of the complex oil suspension. In some embodiments, the mass of the lutein crystals may be 27%-28% of the mass of the complex oil suspension. In some embodiments, the mass of the lutein crystals may be 20%, 22%, 25%, 27%, 30%, 33%, or 35% of the mass of the complex oil suspension.

In some embodiments, the vegetable oil may contain at least one of the following oils: sunflower oil, safflower oil, olive oil, medium chain triglycerides, coconut oil, or corn oil. In some embodiments, the mass of the vegetable oil may be 60%-80% of the mass of the complex oil suspension. In some embodiments, the mass of the vegetable oil may be 62%-78% of the mass of the complex oil suspension. In some embodiments, the mass of the vegetable oil may be 65%-75% of the mass of the complex oil suspension. In some embodiments, the mass of the vegetable oil may be 68%-72% of the mass of the complex oil suspension. In some embodiments, the mass of the vegetable oil may be 60%, 65%, 70%, 75% or 80% of the mass of the complex oil suspension.

In some embodiments, the mass of the phospholipids may be 0.5%-5% of the mass of the complex oil suspension. In some embodiments, the mass of the phospholipids may be 1%-4.5% of the mass of the complex oil suspension. In some embodiments, the mass of the phospholipids may be 1.5%-4% of the mass of the complex oil suspension. In some embodiments, the mass of the phospholipids may be 2%-3.5% of the mass of the complex oil suspension. In some embodiments, the mass of the phospholipids may be 2.5%-3% of the mass of the complex oil suspension. In some embodiments, the mass of the phospholipids may be 0.5%, 1%, 2%, 3%, 4%, or 5% of the mass of the complex oil suspension.

Some embodiments of the application further provide a carotenoid preparation. The carotenoid preparation is obtained by mixing a pretreated carotenoid with a pretreated gelatinized wall material and emulsifying and granulating.

In some embodiments, the carotenoid comprises lutein crystals mentioned above. In some embodiments, the carotenoid may also include zeaxanthin and beta-carotene. In some embodiments, the raw material of the pretreated carotenoid can be prepared by mixing lutein crystals, zeaxanthin and beta-carotene in a weight ratio of (1-3):(1-3):(1-3). In some embodiments, the raw material of the pretreated carotenoid may be prepared by mixing lutein crystals, zeaxanthin and beta-carotene in a weight ratio of (2-3):(1-2):(1-2). In some embodiments, the raw material of the pretreated carotenoid may be prepared by mixing lutein crystals, zeaxanthin and beta-carotene in a weight ratio of (1-2):(1-2):(1-2). In some embodiments, the lutein in the raw material of the pretreated carotenoid may be replaced by a lutein fatty acid ester.

In some embodiments, the carotenoid may include at least one of lutein, lutein fatty acid esters, zeaxanthin, lycopene, alpha-carotene, beta-carotene, keratin, or astaxanthin.

In some embodiments, the pretreated zeaxanthin crystals contain two isomers, (3R,3'R)-zeaxanthin and (3R,3'S)-zeaxanthin, which have a zeaxanthin crystal weight ratio of greater than 80%. In some embodiments, the weight ratio between the two isomers, (3R,3'R)-zeaxanthin and (3R,3'S)-zeaxanthin, is in the range of 5-15%:95-85%.

In some embodiments, the pigment content of the pretreated carotenoid may be greater than 70%. In some embodiments, the pigment content of the pretreated carotenoid may be greater than 80%. In some embodiments, the pigment content of the pretreated carotenoid is more than 90%.

In some embodiments, the amount of pretreated gelatinized wall material used may be 40-80% of the weight of the carotenoid preparation. In some embodiments, the amount of pretreated gelatinized wall material used may be 60-80% of the weight of the carotenoid preparation. In some embodiments, the amount of pretreated gelatinized wall material used may be 65-70% of the weight of the carotenoid preparation. In some embodiments, the amount of pretreated gelatinized wall material used may be 40-70% of the weight of the carotenoid preparation. In some embodiments, the amount of pretreated gelatinized wall material used may be 45-60% of the weight of the carotenoid preparation. In some embodiments, the amount of pretreated gelatinized wall material used may be 50-70% of the weight of the carotenoid preparation.

In some embodiments, the raw material of the pretreated gelatinized wall material may include wall material and carbohydrate. The wall material and the carbohydrate are mixed in a preset weight ratio to prepare an aqueous solution with a first solids content, which is then stirred and dispersed to obtain the pretreated gelatinized wall material.

In some embodiments, the weight ratio of the wall material to the carbohydrate may be 1:(1-5). In some embodiments, the weight ratio of the wall material to the carbohydrate may be 1:(2-4). In some embodiments, the weight ratio of the wall material to the carbohydrate may be 1:(3-4). In some embodiments, the wall material may contain a mixture of starch and cellulose derivatives. Starch refers to a natural polymer compound of a polysaccharide that is formed by the polymerization of glucose molecules. The starch may include, for example, but is not limited to, corn starch, tapioca starch, potato starch and the like. In some embodiments, the wall material may also contain gum arabic. In some embodiments, the carbohydrate may include at least one of the following: sucrose, glucose, glucose syrup, xylose, oligomaltose, oligofructose, corn solid syrup. In some embodiments, the wall material may be a mixture of starch and cellulose derivatives in a weight ratio of 1:(1-2). In some embodiments, the wall material may be a mixture of starch and cellulose derivatives in a weight ratio of 1:(1-1.8). In some embodiments, the wall material may be a mixture of starch and cellulose derivatives in a weight ratio of 1:(1.2-1.5).

In some embodiments, the weight ratio of the wall material to the carbohydrate may be (1-5):1. In some embodiments, the weight ratio of the wall material to the carbohydrate may be (2-4):1. In some embodiments, the weight ratio of the wall material to the carbohydrate may be (3-3.5):1. In some embodiments, the wall material may be modified contain starch. The modified starch is a polymer compound obtained from a starch base through physical, chemical or enzymatic treatments to introduce new functional groups into the starch molecules or to change the size of the starch molecules and the properties of the starch granules. In some embodiments, the modified starch may include, but is not limited to, sodium starch octenyl succinate. In some embodiments, the wall material may also contain gum arabic. In some embodiments, the wall material may also contain a cellulose derivative.

In some embodiments, the carotenoid preparation may have a pigment solubility in water of less than 5%. In some embodiments, the carotenoid preparation may have a pigment solubility in water of less than 4%. In some embodiments, the carotenoid preparation may have a pigment solubility in water of less than 3%. In some embodiments, the carotenoid preparation may have a pigment solubility in water of less than 1%. In some embodiments, the carotenoid preparation may have a pigment solubility in water of less than 0.5%. In some embodiments, the carotenoid preparation may have a pigment solubility in water of less than 0.3%.

In some embodiments, the release level of the carotenoid preparation in gastrointestinal fluid for 0.5 h is less than 35%. In some embodiments, the release level of the carotenoid preparation in gastrointestinal fluid for 0.5 h is less than 30%. In some embodiments, the release level of the carotenoid preparation in gastrointestinal fluid for 0.5 h is less than 25%.

In some embodiments, the release level of the carotenoid preparation in gastrointestinal fluid is greater than 90% for 4 hours. In some embodiments, the release level of the carotenoid preparation in gastrointestinal fluid for 4 hours is less than 95%. In some embodiments, the release level of the carotenoid preparation in gastrointestinal fluid for 4 hours is less than 98%.

In some embodiments, the carotenoid preparation may be used in various fields, including the fields of food, beverages, nutraceuticals, pharmaceuticals, and the like. In some embodiments, the carotenoid preparation may also be used in the manufacture of products requiring a nutrient visualization effect, gummies, solid drinks, liquid drinks, tablets, solid preparations, eye gels or eye drops, and the like.

The beneficial effects that can be brought about by some embodiments of the present application include, but are not limited to: (1) the lutein crystals are prepared using a tubular reaction in combination with an alcoholysis method, which not only shortens the saponification time but also includes the lutein ester converts only a small amount of alkali into lutein, which is environmentally friendly while reducing labor costs and raw material costs; (2) the lutein is obtained by using a complexing agent for purification, which does not require the use of organic solvents for extraction and is environmentally friendly, and the post-treatment process can be effectively reduced to shorten the production time and improve the production efficiency of lutein crystals; (3) the carotenoids are pretreated, the mixture of starch and cellulose derivatives is used as raw materials of the wall material, and the wall material and carbohydrate are used in the weight ratio of 1:(1-5) to prepare the pretreated gelatinized wall material, and on the basis of pretreated carotenoids and the gelatinized wall material, the carotenoid preparation is prepared, which can not only reduce the degree of release of carotenoids in the hydrochloric acid solution to avoid their destruction by gastric acid and maintain the bioactivity of carotenoids, but also can effectively reduce the degree of pigment solubility to achieve the avoid staining of clothing, tongues and hands, etc. when using the carotenoid products; (4) the carotenoids are pretreated, the starch is used as raw materials of the wall material, and the wall material and carbohydrate are used in the weight ratio of (1-5):1 for producing the pretreated gelatinized wall material, and on the basis of the pretreated carotenoids and the gelatinized wall material, the carotenoid preparation is prepared, which can not only reduce the degree of release of carotenoids in the hydrochloric acid solution to avoid their destruction by gastric acid and maintain the bioactivity of carotenoids, while the degree of release in the phosphate buffer solution is greater, which increases the absorption in intestinal favored; but also can effectively reduce the pigment solubility degree to avoid the coloring of clothes, tongues and hands etc. when using the carotenoid products; It should be noted that different versions Examples may produce various beneficial effects, and in various embodiments, the positive effects that may be produced may be one or a combination of more of the above-mentioned beneficial effects, or any of other beneficial effects that may be obtained.

It should be noted that the above embodiments are used only to illustrate the technical solution of the present invention, and are not used to limit the technical solution, and those skilled in the art should understand that they are the technical solutions of the may change or equivalently replace the present invention without departing from the purpose and scope of the technical solution, and such changes or equivalent replacements should be considered as covered by the scope of the claims of the present invention.

At the same time, specific terms are used in the present application to explain exemplary embodiments of the present application. For example, “an embodiment,” “an example,” and/or “some embodiments” shall be understood to refer to a particular feature, structure, or property associated with at least one embodiment of the present application . Accordingly, it should be emphasized and noted that "an example" or "an embodiment" or "an alternative embodiment" mentioned two or more times in different places in the present application do not necessarily refer to the same embodiment. Additionally, certain features, structures, or properties may be appropriately combined in one or more embodiments of the present application.

QUOTES INCLUDED IN THE DESCRIPTION

This list of documents listed by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• CN 106316909 A [0046]
• CN 101260071 A [0048]
• CN 106748947 A [0050]

Claims (11)

Lutein crystal, wherein the lutein crystal is prepared according to the following steps: connecting a first line, a second line and a third line with a “Y”-shaped connecting valve; mixing marigold extract with a low carbon alcohol and feeding the mixture into the first line at a first flow rate and then preheating to obtain a marigold extract solution; feeding the alcohol mixed solution into the second line at a second flow rate, wherein the ratio of the flow rate of the marigold extract solution to that of the alcohol mixture solution is the first flow rate ratio; Mixing the marigold extract solution and the alcohol mixture solution in the third line, Maintaining the third line at a first temperature and pressure and carrying out the saponification reaction to obtain the saponified reaction solution; adding acid to the saponified reaction solution to neutralize it to a first pH, then adding a complexing agent, stirring at room temperature, precipitating lutein crystals and filtering to obtain a first filter cake; and Adding alkaline alcohol solution in the first filter cake, stirring at room temperature and filtering to obtain a second filter cake, adding water in the second filter cake, stirring, filtering and drying to obtain a lutein crystal. Lutein crystal Claim 1 , wherein the low carbon alcohol may comprise a low carbon C1-C4 alcohol. Lutein crystal Claim 1 , wherein the alcohol mixed solution contains at least one of the following solutions: sodium ethoxide-ethanol solution, sodium methoxide-methanol solution, potassium methoxide-methanol solution, potassium ethoxide-ethanol solution, sodium hydroxide-alcohol solution, potassium hydroxide-alcohol solution. Lutein crystal Claim 1 , where the first flow rate ratio is in the range of 1:(1-5). Lutein crystal Claim 1 , whereby the mass ratio of the complexing agent to the marigold extract is in the range of (0.0005-0.01):1. Complex oil suspension, wherein the complex oil suspension contains a lutein crystal according to one of the Claims 1 until 5 , vegetable oil and phospholipids, wherein the mass of the lutein crystal constitutes 20%-35% of the mass of the complex oil suspension, and wherein the mass of vegetable oil constitutes 60%-80% of the mass of the complex oil suspension, and wherein the mass of the phospholipid is 0.5 %-5% of the mass of the complex oil suspension. Complex oil suspension after Claim 6 , wherein the vegetable oil contains at least one of the following oils: sunflower oil, safflower oil, olive oil, medium chain triglycerides, coconut oil or corn oil. Carotenoid preparation, wherein the carotenoid preparation is prepared by mixing, emulsifying and pelleting pretreated carotenoids and pretreated gelatinized wall material, the carotenoids forming a lutein crystal according to one of the Claims 1 until 5 include. Carotenoid preparation after Claim 8 , wherein the carotenoid further comprises zeaxanthin and beta-carotene, and wherein the raw material of the pretreated carotenoid is prepared by mixing lutein crystals, zeaxanthin and beta-carotene in a weight ratio of (1-3):(1-3):(1-3). becomes. Carotenoid preparation after Claim 8 , where the pigment content of the pretreated carotenoid is more than 70%. Carotenoid preparation after Claim 8 , where the amount of pretreated gelatinized wall material used is 40-80% of the weight of the carotenoid preparation.

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